Fuel additives



United States Patent cc FUEL ADDITIVES John D. Bartleson, Franklin,Mich.,.assignor to Ethyl Corporation, New York, N.Y., a corporation ofDelaware No Drawing. Application January 29, 1954 Serial N0. 407,165

8 Claims. (Cl. 44-69) This invention relates to novel compositionscomprising organophosphorus materials and minor proportions of an amineand to uses thereof. This application is a continuation-in-part of myprior applications, Serial Nos. 374,151 and 374,156, both filed August13, 1953, now Patent Nos. 2,794,718 and 2,794,713 respectively, bothgranted June 4, 1957.

2,935,390 Patented May 3, 1960 taining fuels, especially those used inspark ignition type internal combustion engines, having improvedsolubility characteristics and stability against the adverse affects ofdeteriorative environments during compounding, blending and storage. Itis also an object of this invention to provide improved compositionscomprising a hydro- When leaded fuels are utilized in internalcombustion,

engines, there is an accumulation of deposits in the combustion chamberswhich results in a number of serious problems including deposit-inducedautoignition or wild ping, spark plug fouling, reduction in exhaustvalve life and the like. The magnitude of these problems is intensifiedeach time the lead concentration in the fuel is raised to coincide withincrease in compression ratio of internal combustion engines inpassenger cars and trucks. v

A method for modifying engine deposits and decreasing their ill effectsby utilizing phosphorus-containing materials has been proposed in theprior art. For example, it has been shown that certainorganophosphorus-containing materials such as those obtained by thereaction of a phosphorus sulfide with an olefinic hydrocarbon (SerialNo. 374,151 noted above), and'the product obtained by reaction between aphosphorus sulfide and an active hydrogen-containing aromatic compound(Serial No. 374,156 noted above), when used as fuel additives, resultedin the diminution of deposit-induced engine problems. However, it wasfound that such phosphoruscontaining materials, while not in the strictsense of the word insoluble in gasoline, do, upon addition to gasolines,form incomplete solutions typified by the creation of a haze or otherindications of a colloidal dispersion. Furthermore, it was also foundthat the phosphorus-containing materials discussed above were notcompletely soluble in tetraethyllead-containing fluids and on standingresulted in the deposition of a heavy white sludge. It is seen,therefore, that aneed exists for a composition of matter comprisingphosphorus-containing materials possessing increased solubility andstability in order that they may be added to fuels and to fluidscontaining organolead compounds, scavengers and other components,without any harmful effects.

It is, therefore, an object of this invention to provide novelorganophosphorus-containing materials possessing enhanced stability. andsolubility characteristics. It is likewise, an object of the presentinvention to provide novel compositions of matter comprising the productobtained by the reaction between a phosphorus sulfide and a hydrocarbon,and a minor portion of a basic amine. Another object of this inventionis to provide means of improving compositions such as antiknock fluidsand fuels which contain organolead antiknock agents and organophosphoruscompounds by incorporating a small amount of a basic amine therein.Another object of this invention is to provide improved organoleadcompositions such as anti-knock fluidsand organolead-com carbon fuel, anorganophosphorus compound and a minor proportion of a basic amine.Another object is to provide improved fuel composition which, when usedin spark-fired internal combustion engines, simultaneously alleviatespark plug fouling and increase exhaust valve life. Other importantobjects of this invention will be apparent from the discussion whichfollows. I

It hasbeen found that the above and other objects of this invention areobtained by providing compositions of matter comprising the productobtained by reaction between a phosphorus sulfide and a hydrocarbonselected from the group consisting of an active hydrogen-containingaromatic compound and an olefinic hydrocarbon, and a minor amount of abasic amine having a dissociation constant characteristic of a base ofnot less than about 1 10 I have also found that when organophosphoruscompounds which are not completely soluble in fuels, are added to suchfuels in the form of the novel compositions of matter of this invention,they are completely soluble therein and no haze or precipitate formseven after prolonged storage.

I have also discovered that the compositions of matter of my inventioncan be readily blended with organolead antiknock fluids. Such organoleadfluids containing organophosphorus and amine components show no signs ofdecomposition of the organolead compound. This is in contrast to thecase where organophosphorus compounds are added without any amine,whereupon a heavy white precipitate slowly settles out indicating thatthe phosphorus compound causes the organolead compound to slowlydecompose.

In like manner, the composition of this invention comprising anorganophosphorus compound and abasic amine having a dissociationconstant characteristic of a base of not less than about 1X10 can beblended with fuels containing organo antiknock fluids. The presence ofthe amine in this composition prevents the destruction of the organoleadcompound by the phosphorus compound.

. The resulting fuel is thus endowed with the beneficial base of notless than about 1 10- and the product obtained by the reaction betweensuch compounds as phosphorus pentasulfide (P 8 (P 8 phosphorusheptasulfide (P 8 and the like, and an olefinic hydro carbon or anactive hydrogen-containing aromatic compound, that is, a compound whichcontains at least one aryl radical and a hydrogen atom activatedthereby.

An embodiment of this invention is the product obtained by the reactionof a basic amine of the type described previously with the reactionproduct of a phosphorus sulfide andan olefinic polymer having amolecular weight in the range of from about 100 to about 500. Oneexample of an olefinic material that can be used is the hydrocarbonfraction of an olefinic gasoline made by the polymerization ofpropylenes and butylenes by known methods from which have been removedall components enes.by.known methodsv This polymer hasan. ayeragei;

boiling below 250 F. The average molecular weight of such an olefin isabout 140. Another olefinic polymer employed is. one obtained bypolymerizing mixed butylmolecular weight of about 420. An illustrativeexample of the trihydrocarbon substituted methanes used in thepreparation of the organophosphorus compounds employed in this inventionis isopropylbenzene.

The organophosphorus compounds discussed above are formed by using fromabout 0.2 to about 2.0 moles of phosphorus sulfide per mole of anolefinic hydrocarbon or an active hydrogen-containing aromatic compoundin the reaction.

Although, as will be shown later, the effect obtained is not due to themere addition of a base, it has nevertheless been found that the maximumbeneficial results are obtained when the dissociation constant,characteristic of a base, of the amine used is not less than about l Theamine or amines can be aliphatic, alicyclic or heterocyclic, primary orsecondary, containing about 5 to about 36 carbon atoms. The aliphaticamines can be straight or branched chain as for example, amylamine,octylamine, dibutylamine, the diamylamines both straight and branchedchain, diisopropylamine, ethylpropylamine, isopropylbutylamine,dodecylamine, dioctadecylamine, and the like. Examples of alicyclicamines are piperidine and the like. The aromatic amines can beillustrated by such examples as pyridine, quinoline and the like. Anyone of the above types of amines or a mixture of two or more of suchamines can be used in my invention in cornbination with anorganophosphorus sulfide reaction prodnet or of mixtures of various suchorganophosphorus products to make my novel compositions of matter.

I have also found that only a small proportion of amine need be presentin my new composition of matter to obtain the beneficial effectsdesired. For example, very good results are obtained when the amine ispresent in the weight ratio of from about 0.0129 to about 0.065nitrogen-to-phosphorus on the basis of the phosphorus in thephosphorus-containing reaction product. While the above is a preferredembodiment I can, in fact, use greater amounts of the amine or amines.However, the beneficial effect observed relative to the proportion ofamine added over and above the ratio of 0.065 nitrogen-to-phosphorus,rapidly diminishes so that the practical upper limit on the amount usedis such that the nitrogen-to-phosphorus ratio is 0.129.

That the beneficial effects observed on employing the compositions ofthe invention are not merely the result of a neutralization of acidicgroups in the organophosphorus compounds is evidenced by the fact thatneutralization of said organo-phosphorus compounds with an alkalibicarbonate and removal of the water soluble salts does not improve theresulting product with respect to stability and solubility as will beshown hereinbelow. On the other hand, the mere addition of approximately2 percent of an amine, of the kind described above, to a reactionproduct of a phosphorus sulfide and an olefin or an activehydrogen-containing aromatic compound, renders the resulting materialsoluble in fluids and fuels which can contain organolead compounds, andin which there can also be present other components such as scavengers,dyes and solvents such as kerosene and the like which are of the natureof those employed in antiknock fluids. To illustrate, it has been foundthat when a phosphorus sulfide-olefin reaction product, which has beentreated with a bicarbonate wash, is dissolved in a fluid or fuelcontaining an organolead compound and allowed to stand for a shortperiod of time, there settles out a heavy white sludge, which isprobably due to some reaction between the phosphorus sulfur-containingcompound and the organolead compound, resulting in a decomposition ofthe latter. On the other hand, when a small amount of an amine is addedto the phosphorus sulfur-containing compound either before or shortlyafter adding the latter to the organolead composition, it is noticedthat no sludge settles out even after standing a considerable length oftime. This is true of the amine addition regardless of whether thephosphorus sulfur-contain-v ing compound has or has not been treatedwith a bicarbonate wash. These observations appear to indicate that theadded amine reacts with certain functional groups in the phosphorus andsulfur-containing organic product to form a type of chemical bond orelectron configuration different from that in other superficiallyrelated base neutralized products. That the phenomena observed, namely,the solubilization of the'phosphorus sulfur-containing product and theprevention of sludge formation, is not due to the solvent action of theamine per se, was evidenced by the fact that the addition of the amineafter the sludge had formed did not result in the re-dissolving of saidsludge.

In order to demonstrate the beneficial effect of employing a smallamount of an amine in conjunction with the phosphorus sulfur-containingorganic compound in solutions containing organolead compounds togetherwith scavengers, dyes and the like, such as organolead antiknock fluidsand fuels, a number of tests were conducted both with and without theamine being present. The results of these tests are contained in theexamples given below.

The term theory is used in the examples in denoting the amount ofhalogen and of phosphorus present. A theory of a halogen is defined asthe theoretical amount of halogen required to react with the leadpresent to form lead dihalide. One theory of phosphorus is defined asthat amount of phosphorus required to combine with a given amount oflead to form Pb (PO Alternatively, a theory of a halogen is defined asthat amount of halogen being present which corresponds to an atom ratioof 2:1 halogen-to-lead. Similarly, a theory of phosphorus is that amountof phosphorus which corresponds to an atom ratio of 2:3phosphorusto-lead.

The following examples more specifically illustrate the methods ofblending and the beneficial effects obtained by my new compositions ofmatter.

Example I To 49 parts by weight of the product obtained by the reactionof P S with a hydrocarbon fraction of an olefinic gasoline made by thepolymerization of propylenes and butylenes by known methods and fromwhich the components boiling below 250 F. have been removed, is addedone part of dodecylamine. The two components are then subjected toagitation by means of stirring until a homogeneous mixture is obtained.This constitutes one method of making the new compositions of matter ofmy invention.

While in the above example no heat is required for the reaction of theamine with the organophosphorus compound, it may sometime be foundadvantageous to apply heat while agitating the mixture in order tohasten or aid the reaction. This will, of course, depend on theparticular amine and the organophosphorus compound employed.

Example II To 40 parts by weight of a petroleum hydrocarbon fuelavailable as an article of commerce is added one part of the compositionof Example I. The mixture is agitated by means of stirring until ahomogeneous solution results. No haziness is observed in the fuelblended in this manner and standing for a period of thirty days does notresult in the formation of any precipitate, thus illustrating thebeneficial effect of the compositions of matter of this invention.

Example III To 32 parts by weight of conventional antiknock fluidcontaining 19.7 parts of tetraethyllead, 0.5 theory of bromine asethylene dibromide and 1.0 theory of chlorine as ethylene dichloride,together with kerosene and a dye, is added 0.2 theory of phosphorus inthe form of the composition of Example I. The mixture is thor- To 300parts by weight of a petroleum hydrocarbon fuel available as an articleof' commerce is added 1 part of the composition of Example III. Onstirring until a homogeneous mixture results, it is found that nocloudiness appears and allowing the solution to stand for more thanthirty days does not result in the formation of any precipitate.

Example V One part of P S -olefin reaction product was added to 2700parts by weight of a petroleum hydrocarbon fuel of the gasoline boilingrange which contained 8 parts of conventional antiknock fluid. Themixture was thoroughly stirred but the 'organophosphorus compound wouldnot go into solution, remaining in the form of a cloudy dispersion whichslowly settled out. To this mixture was next added 2% by weight ofdodecyl amine, based on the amount of the organophosphorus substancespresent. The mixture was again thoroughly agitated and it was found thata clear solution resulted with no sediment formation even after standingfor 10 days.

Example VI To 40 parts by weight of a petroleum hydrocarbon fuelavailable as an article of commerce was added one part of the productobtained by the reaction of P 8 with a hydrocarbon fraction of anolefinlc gasoline made by the polymerization of propylenes and butylenesfrom which the components boiling below 250" F. had been removed.Immediately upon addition a haze formed. and a precipitate separatedslowly. To this solutionwas then added 2% of dodecylamine based upon theweight of the phosphorus sulfide-olefin reaction prod-, uct. Theaddition of the amine dissipated the haze or precipitate from thesolution and it did not reappear even after standing for a period ofover 20 days. Thisillustrates the remarkable. effectiveness of a verysmall amount of an amine on the solubility of the phosphoruscontainingcompound.

Example VII To 32 parts of conventional antiknock fluid containing 19.7parts of tetraethyllead, 0.5 theory of bromine as ethylene dibromide and1.0 theory of chlorine as ethylene dichloride, together with keroseneand a dye, was added 0.1 theory of phosphorus as the P S -olefinreaction product which had been treated with a potassium bicarbonatewash. On first addition the solution was clear but on standing, aheavy'white precipitate settled out. After allowing this solution tostand for three days, 2% of dodecylamine, based upon the weight of theorganophosphorus compound present, was added. The resulting solution wassubjected to agitation but the white precipitate would not go intosolution.

. ExampleV III To 32 parts of conventional tetraethyllead antiknockfluid described in Example VII was added 0.2 theory of phosphorus as theP S -olefin reaction product. -On first 6 6 Example IX To 32 parts oftetraethyllead fluid described in Example VII was added 0.2 theory ofphosphorus as the olefin reaction product which had been treated with apotassium bicarbonate wash. The solution was clear on first addition butupon standing for 30 minutes it became cloudy. Two percent ofdodecylamine based upon the weight organophosphorus compound was thenadded. The cloudiness disappeared and on standing for five days therewas no evidence of any white precipitate or sludge being formed.

Example X To 32 parts of conventional antiknock fluid containing 19.7parts of tetraethyllead, 0.5 theory of bromine as ethylene dibromide and1.0 theory of chlorine as ethylene dichloride, the theories of halogenbeing based upon the amount of lead present in the form oftetraethyllead, and kerosene together with a dye, was added 0.1 theoryof phosphorus as the P S -olefin reaction product. The solution becameturbid immediately upon the addition of the organophosphorus compound.-To this solution was then added 2% dodecylamine based upon the weightofthe organophosphorus compound present. The turbidity disappeared fromthe solution. The mixture was allowed to stand for 10 days during whichtime no change was noted in its appearance. No white precipitate wasformed.

The foregoing examples illustrate the fact that a small amount of theamine is essential to render the organophosphorus compounds of the typediscussed previously in this application, soluble and stable in fuelsand in conventional organolead antiknock fluids. Example VII, givenabove, illustrates that treating a P S -olefin reaction product with abicarbonate wash does not, on addition of the product to the antiknockfluid, render the solution stable. However, Examples II, III, IV, V, VI,VIII, IX and X illustrate the fact that regardless of whether or not theorganophosphorus compound was treated with a bicarbonate solution, theaddition of a small amount of a basic amine not only makes theorganophosphorus compound soluble in fuel and in conventional organoleadantiknock fluid but the amine imparts a stabilizing influence whichinhibits reaction with, and decomposition of the organolead compound andthus prevents the formation of the white precipitate.

,It is also seen from the examples given above that there are severalways in which the new compositions of my invention can be utilized. Forinstance, the amine can be added to the organophosphorus compound beforethe. addition to the fuel or fluid as in Examples II and III, or'firstone component can be added and then the other as in Examples V, VI,VIII, IX and X. Another alternative is to add the two componentssimultaneously.

Fuel compositions described in Examples IV and V were each used as afuel in a standard six-cylinder automotive engine. It was found that agreat reduction in spark plug fouling as well as a substantial increasein exhaust valve life was achieved, as compared to eflects observed whenthe improved organophosphorus-amine compositions of this invention werenot included in the fuel.

Although the antiknock fluid used in the examples with the fuels willdepend on the use for which it is required. For instance, it will varyfrom about 1.58 to about 3.17 grams of lead per gallon in the form oftetraethyllead when used in automobile engines, and up to as high asabout 6.4 grams of lead per gallon when used in fuels for aviationengines. However, concentrations slightly above and below those recitedcan be used if conditions so require.

In all the compositions wherein the organophosphorus and aminecompositions of the present invention are utilized, the amount ofphosphorus present is from about 0.1 to about 0.35 theory, based on theamount of lead present, which is equivalent to an atom ratio of fromabout 0.2:3 to about 0.7 :3 phosphorus-to-l'ead. When no lead is presentthe organophosphorus compound can be employed in the fuel in amountsequivalent to from about 0.016 to about 0.23 gram of phosphorus per galon of fuel. The amine as stated previously is employed in the weightratio of from about 0.0129 to about 0.129 nitrogen-to-phosphorus on thebasis of the phosphorus present as the organophosphorus compound.

The improved combined organophosphorus and amine product of thisinvention can be effectively utilized by supplemental injection inthe-internal combustion engines and in dual fuel systems for theeffectiveness desired from such use, as described in my co-pendingapplications mentioned hereinbefore. Likewise, concentrated fuelscontaining varying amounts of organolead antiknock compounds andcombined organophosphorus and amine products of my invention forinternal combustion engines can be utilzed in this manner.

The organophosphorus-amine of this invention can be used in antiknockfluids and fuels containing various halide scavengers such asethylenedibromide, ethylenedichloride, mixed dibromotoluenes,trichlorobenzenes, and in general such organic halide scavengers asthose disclosed in US. 1,592,954; 1,668,022; 2,364,921; 2,398,281;2,479,900; 2,479,901; 2,479,902; 2,479,903; and 2,496,983. Likewise, theadjuvants of this invention can be used in conjunction with other motorfuel additives such as antioxidants, organolead stabilizers, organicdyes, solubilizers, and indeed with other catalytically active materialsfrequently employed in fuel.

Having fully described the nature of the present invention, the needtherefor, and the best mode devised for carrying it out, it is notintended that this invention be limited except within the spirit andscope of the appended claims.

I claim:

1. An antiknock fluid composition for use as an adjuvant forhydrocarbons of the gasoline boiling range and which consistsessentially of an organolead antiknock agent, a halohydrocarbonscavenger for said agent and a product obtained by reaction between (a)a phosphorus sulfide selected from the group consaid product being insaid composition in amount such that the phosphoruszlead atom ratio isfrom about 0.2:3 to about 07:3.

2. An antiknock fluid consisting essentially of tetraethyllead, ascavenging agent for said tetraethyllead, said scavenging agent beingselected from the group consisting of ethylene dichloride, ethylenedibromide and mixtures thereof, and a reaction product of (a) aphosphorus sulfide selected from the group consisting of P S and P487,

(b) an olefinic hydrocarbon polymer having a molecular weight in therange of from about to about 500,

(c) an amine containing about 5 to about 36 carbon atoms and having adissociation constant characteristic of a base of not less than about 110' said product being in said composition in amount such that thephosphoruszlead atom ratio is from about 0.2:3 to about 0.713; and saidamine being present in said reaction product in amount such that theweight ratio of nitrogen to phosphorus is from about 0.0129 to about0.129 based on the phosphorus contained in said product.

3. The composition of claim 1 wherein said amine is dodecyl amine.

4. Hydrocarbon fuel of the gasoline boiling range adapted for use inspark ignition internal combustion engines, said fuel containing thecomposition of claim 1 in an amount such that the composition providesfrom about 1.58 to about 6.4 grams of lead per gallon of the fuel.

5. The composition of claim 2 further characterized in that said polymerused to form said product is ob tained by the polymerization ofpropylenes and butylenes and has an average molecular weight of about140.

6. Hydrocarbon fuel of the gasoline boiling range adapted for use inspark ignition internal combustion engines, said fuel containing thecomposition of claim 2 in an amount such that the composition providesfrom about 1.58 to about 6.4 grams of lead per gallon of the fuel.

7. Hydrocarbon fuel of the gasoline boiling range adapted for use inspark ignition internal combustion engines, said fuel containing thecomposition of claim 3 in an amount such that the composition'providesfrom about 1.58 to about 6.4 grams of lead per gallon of the fuel.

8. Hydrocarbon fuel of the gasoline boiling range adapted for use inspark ignition internal combustion engines, said fuel containing thecomposition of claim 5 in an amount such that the composition providesfrom about 1.58 to about 6.4 grams of lead per gallon of the fuel.

References Cited in the file of this patent UNITED STATES PATENTS2,137,584 Ott Nov. 22, 1938 2,316,082 Loane et al. Apr. 6, 19432,398,281 Bartholomew Apr. 9, 1946 2,405,560 Campbell Aug. 13, 19462,507,731 Mixon et al May 16, 1950 2,534,217 Bartleson Dec. 19, 19502,636,858 Jones et al. Apr. 28, 1953 2,712,528 Hill et a1. July 5, 19552,734,863 Jones et a1. Feb. 14, 1956 FOREIGN PATENTS 683,405 GreatBritain Nov. 26, 1952

2. AN ANTIKNOCK FLUID CONSISTING ESSENTIALLY OF TETRAETHYLLEAD, ASCAVENGING AGENT FOR TETRAETHYLLEAD, SAID SCAVENGING AGENT BEINGSELECTED FROM THE GROUP CONSISTING OF ETHYLENE DICHLORIDE, ETHYLENEDIBROMIDE AND MIXTURES THEREOF, AND A REACTION PRODUCT OF (A) APHOSPHROUS SULFIDE SELECTED FROM THE GROUP CONSISTING OF P2S5 AND P4S7,(B) AN OLEFINIC HYDROCARBON POLYMER HAVING A MOLECULAR WEIGHT IN THERANGE OF FROM ABOUT 100 TO ABOUT 500, (C) AN AMINE CONTAINING ABOUT 5 TOABOUT 36 CARBON ATOMS AND HAVING A DISSOCIATION CONSTANT CHARACTERISTICOF A BASE OF NOT LESS THAN ABOUT 1X10**-9, SAID PRODUCT BEING IN SAIDCOMPOSITION IN AMOUNT SUCH THAT THE PHOSPHORUS: LEAD ATOM RATIO IS FROMABOUT 0.2:3 TO ABOUT 0.7:3, AND SAID AMINE BEING PRESENT IN SAIDREACTION PRODUCT IN AMOUNT SUCH THAT THE WEIGHT RATIO OF NITROGEN TOPHOSPHORUS IS FROM ABOUT 0.0129 TO ABOUT 0.129 BASED ON THE PHOSPHORUSCONTAINED IN SAID PRODUCT.
 5. THE COMPOSITION OF CLAIM 2 FURTHERCHARACTERIZED IN THAT SAID POLYMER USED TO FORM SAID PRODUCT IS OBTAINEDBY THE POLYMERIZATION OF PROPYLENES AND BUTYLENES AND HAS AN AVERAGEMOLECULAR WEIGHT OF ABOUT 140.